JP5941429B2 - Polyamic acid and polyimide - Google Patents

Description

  The present invention relates to a polyamic acid and a polyimide obtained by polymerizing a specific aromatic diamine compound and two kinds of aromatic tetracarboxylic acid compounds.

  Aromatic polyimides obtained by condensation polymerization of aromatic tetracarboxylic acid compounds and aromatic diamine compounds are superior in mechanical strength, heat resistance, electrical insulation, chemical resistance, etc. Widely used in applications such as equipment materials.

  Conventionally used polyimide materials include: paraphenylenediamine (PDA) -biphenyltetracarboxylic acid (BPDA) polyimide, 4,4′-diaminodiphenyl ether (ODA) -pyromellitic dianhydride (PMDA) Two-component polyimides such as polyimide, and three-component and four-component polyimides obtained by copolymerizing the above monomers at an arbitrary ratio have been proposed.

  Aromatic polyimides as described above have excellent properties such as very high mechanical strength, heat resistance, chemical resistance and insulating properties due to their rigid molecular structure and strong interaction of imide bonds connecting them. However, on the other hand, due to its molecular structure and intermolecular interaction, it has poor solvent solubility, and can only be molded in the form of a polyamic acid varnish, which is a precursor, to form, and forms an imide bond with the solvent during heat curing. The generation of condensed water is a drawback in processing.

  In order to impart solvent solubility to such aromatic polyimide, it is an effective means to introduce a monomer having a flexible bond or a highly soluble functional group. An imide (Patent Document 1) and a polyetherimide (Patent Documents 2 and 3) into which an ether bond is introduced are known.

Japanese Patent No. 2537179 U.S. Pat. No. 3,847,867 U.S. Pat. No. 3,847,869

  However, general soluble polyimides such as those shown in Patent Documents 1 to 3 have a mechanical strength of a molded product, particularly toughness (elongation) because the molecular structure of the constituent monomers is too flexible and the degree of polymerization of the polymer is low. Rate) tends to be low.

  As a result of earnest research to solve the above problems, the present inventor has found that 4,4′-oxydiphthalic anhydride (ODPA) and 3,3 ′, 4,4′-biphenyltetracarboxylic acid in the aromatic tetracarboxylic acid component. It has been found that a polyimide molded body can be toughened by polymerizing dianhydride (BPDA) at a specific quantitative ratio.

That is, this invention provides the following 1-4.
(1) A diamine component composed of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 4,4′-oxydiphthalic anhydride: 80 mol% or more , less than 90 mol%, and 3,3 ′ , 4,4′-biphenyltetracarboxylic dianhydride: Polyamic acid obtained by polymerizing an acid component composed of 20 mol% or less and more than 10 mol%.
(2) A diamine component composed of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 4,4′-oxydiphthalic anhydride: 80 mol% or more , less than 90 mol%, and 3,3 ′ , 4,4′-biphenyltetracarboxylic dianhydride: A polyamic acid composition containing a polyamic acid obtained by polymerizing an acid component composed of 20 mol% or less and more than 10 mol%.
(3) 4,4′-oxydiphthalic anhydride: 80 mol% or more , less than 90 mol%, and 3,3 ′ to a diamine component composed of 2,2-bis [4- (4-aminophenoxy) phenyl] propane , 4,4′-biphenyltetracarboxylic dianhydride: A polyimide obtained by polymerizing an acid component consisting of 20 mol% or less and more than 10 mol%.
(4) 4,4'-oxydiphthalic anhydride: 80 mol% or more , less than 90 mol% and 3,3 'in a diamine component composed of 2,2-bis [4- (4-aminophenoxy) phenyl] propane , 4,4′-biphenyltetracarboxylic dianhydride: A polyimide composition containing a polyimide obtained by polymerizing an acid component consisting of 20 mol% or less and more than 10 mol%.

  The polyamic acid and polyimide of the present invention have high mechanical strength of the resulting polyimide molded body while maintaining high solvent solubility.

The present invention will be described in detail below.
<1. Polyamic acid (polyamic acid composition)>
The polyamic acid of the present invention comprises 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) as an aromatic diamine compound and 4,4′-oxydiphthalic anhydride as an aromatic tetracarboxylic acid compound. (ODPA): 80 mol% or more and less than 90 mol%, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA): by polymerizing 20 mol% or less and more than 10 mol% The resulting polyamic acid.
Polyamic acid is not particularly limited with respect to its molecular structure. For example, a random copolymer, an alternating copolymer, and a block copolymer can be exemplified depending on the polymerization conditions.
The present invention is also a polyamic acid composition containing this polyamic acid.
The polyamic acid composition of the present invention is a composition containing at least one selected from the solvent, dehydrating agent, catalyst, unreacted material, etc. used in the production in addition to the polyamic acid described below. May be. Or, if necessary, addition of solvents, oxidation stabilizers, fillers, adhesion promoters, silane coupling agents, photosensitizers, photopolymerization initiators, sensitizers, end-capping agents, crosslinking agents, etc. to polyamic acid The product can be added to form a polyamic acid composition.
The polyamic acid contained in the polyamic acid composition of the present invention can be used alone or in combination of two or more.

The polyamic acid of the present invention and the polyamic acid composition of the present invention have high solvent solubility and toughness by introducing an aromatic tetracarboxylic acid compound having a biphenyl skeleton in the aromatic tetracarboxylic acid compound at a specific quantitative ratio. And can solve the problems of the prior art.
The inventor of the present application has found that the mechanical strength (particularly toughness) can be improved by introducing BPDA in a specific amount into the polyamic acid and the soluble polyimide obtained from the polyamic acid.
That is, according to the present invention, from the viewpoint that the aromatic tetracarboxylic acid component used when polymerizing polyamic acid is excellent in high solvent solubility, mechanical strength, chemical resistance, hygroscopicity, insulation, etc., 4, 4 ′ -Oxydiphthalic anhydride (ODPA) and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA).

In the present invention, the aromatic tetracarboxylic acid compound component used in polymerizing the polyamic acid is 2,2-bis [4 as an aromatic diamine compound from the viewpoint of achieving both high solvent solubility and high mechanical strength. -(4-aminophenoxy) phenyl] propane (BAPP) and 4,4′-oxydiphthalic anhydride (ODPA) as an aromatic tetracarboxylic acid compound: 80 mol% or more , less than 90 mol%, and 3,3 ′ , 4,4′-biphenyltetracarboxylic dianhydride (BPDA): 20 mol% or less , and more than 10 mol%.

In the aromatic tetracarboxylic acid compound component, if the ratio of BPDA is smaller than the above, it is not preferable because the effect of improving the mechanical strength by introducing BPDA is reduced in the obtained polyimide. Further, if the ratio of BPDA is larger than the above, it is not preferable because the solvent solubility is lowered and the mechanical strength is lowered.
The amount of ODPA in the aromatic tetracarboxylic acid component is 80 mol% or more and less than 90 mol%, and 80 mol% or more and 85 mol% from the viewpoint of achieving both high solvent solubility and high mechanical strength. The following is preferable.
The amount of BPDA in the aromatic tetracarboxylic acid component is 20 mol% or less , more than 10 mol%, 20 mol% or less , 15 mol% from the viewpoint of achieving both high solvent solubility and high mechanical strength. The above is preferable.

One preferred embodiment of the polyamic acid composition of the present invention further contains a solvent. Examples of the solvent that can be contained in the polyamic acid composition of the present invention include N-methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP), N, N-dimethylacetamide, dimethyl sulfoxide, and N, N-diethyl. Examples include acetamide, N, N-dimethylformamide, N, N-diethylformamide, and dimethylsulfone, and these are preferably used alone or in combination.
You may contain the solvent used at the time of superposition | polymerization of a polyamic acid as it is.

<2. Method for producing polyamic acid>
The production of the polyamic acid composition of the present invention (polyamic acid of the present invention) is 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) and 4,4 as aromatic tetracarboxylic acid compound. 4'-oxydiphthalic anhydride (ODPA): 80 mol% or more and less than 90 mol%, and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA): 20 mol% or less , 10 mol There is no particular limitation except that more than% is polymerized.
One preferred embodiment is that a solvent is further used in producing the polyamic acid composition of the present invention (polyamic acid of the present invention). For example, it can be obtained by adding an acid component and a diamine component in a solvent, mixing them into a mixture, and polymerizing the mixture. The acid component and the diamine component can be used in amounts that are approximately equimolar. The mixture can further contain additives as described later, if necessary.

The conditions for polymerizing the mixture are not particularly limited. For example, a mixture obtained by adding BAPP, ODPA, and BPDA to N-methyl-2-pyrrolidone (NMP) is stirred at room temperature to 50 ° C. under atmospheric pressure to react with polyamic acid. A method for producing a solution (polyamic acid composition) of
It is preferable to prepare the polyamic acid (copolymerized polyamic acid) obtained by the above production method at a ratio (concentration) of 10 to 40% by mass in the solvent.

The polyamic acid composition of the present invention can further contain an additive. Examples of the additive include a dehydrating agent and a catalyst used to cyclize the polyamic acid to form a polyimide.
Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as phthalic anhydride, and these are preferably used alone or in combination.
Examples of the catalyst include heterocyclic tertiary amines such as pyridine, picoline and quinoline, aliphatic tertiary amines such as triethylamine, and aromatic tertiary amines such as N, N-dimethylaniline. These are preferably used alone or in combination.

The method for using the polyamic acid composition of the present invention is not particularly limited. For example, the solvent can be removed from the polyamic acid composition of the present invention to form a film. The method for forming the film is not particularly limited. For example, a conventionally well-known method is mentioned.
The polyamic acid composition of the present invention (polyamic acid of the present invention) can be cured to produce a polyimide composition (polyimide).

<3. Polyimide, polyimide composition>
The polyimide of the present invention is obtained by cyclizing the above polyamic acid.
The polyimide composition of the present invention comprises 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) and 4,4′-oxydiphthalic anhydride (ODPA) as an aromatic tetracarboxylic acid compound: 80 mol% or more , less than 90 mol% and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA): Contains polyimide obtained by polymerizing 20 mol% or less and more than 10 mol% It is a polyimide composition.
The diamine component and the acid component used when producing the polyimide composition of the present invention are the same as the components of the polyamic acid of the present invention.
The polyimide contained in the polyimide composition of the present invention corresponds to the polyimide of the present invention.
Regarding the production of the polyimide composition of the present invention (polyimide of the present invention), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) and 4,4 as an aromatic tetracarboxylic acid compound are used. '-Oxydiphthalic anhydride (ODPA): 80 mol% or more and less than 90 mol% and 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA): 20 mol% or less and more than 10 mol% There are no particular restrictions except for polymerizing the.
The molecular structure of the polyimide of the present invention is not particularly limited. For example, a random copolymer, an alternating copolymer, and a block copolymer can be exemplified depending on the polymerization conditions.
The polyimide contained in the polyimide composition of the present invention can be used alone or in combination of two or more.

<4. Manufacturing method of polyimide composition (polyimide)>
For example, the polyimide composition can be produced by adding the above acid component (aromatic tetracarboxylic acid component) and diamine component (aromatic diamine component) to a solvent, mixing them into a mixture, and polymerizing the mixture. Can be obtained.
The polyimide composition of the present invention (polyimide of the present invention) can be produced by direct polymerization using a mixture, or can be produced by cyclizing the polyamic acid composition of the present invention or the polyamic acid of the present invention. it can.
Examples of a method for cyclizing a polyamic acid to form a polyimide include a chemical ring closure method in which dehydration is performed using a dehydrating agent and a catalyst, and a thermal ring closure method in which thermal dehydration is performed. The dehydrating agent and catalyst used in the chemical ring closure method are the same as those described in the method for producing the polyamic acid.

<5. Polyimide solution (varnish)>
Varnish (temporary lacquer) is a transparent and hard top coat (paint) used to protect the surface of a material. The varnish of the present invention refers to a polyimide solution, but also includes a product obtained by applying a polyimide precursor (polyamic acid) varnish (solution), followed by drying and imidization. The polyimide varnish can be used as a top coat and can be used to produce a polyimide film or a polyimide powder.

<6. Polyimide film, polyimide powder>
A method for producing a polyimide film will be described. A solution (varnish) of the polyimide precursor is cast on a substrate such as an insoluble polyimide film, glass, copper, aluminum, stainless steel, or silicon, and dried in an oven. The polyimide film of the present invention can be produced by heating the obtained polyimide precursor film on a substrate in a vacuum, in an inert gas such as nitrogen, or in the air. The imidization is desirably performed in vacuum or in an inert gas, but may be performed in air if the imidization temperature is not too high.
The imidation reaction can also be performed by immersing the polyimide precursor film in a solution containing a dehydrating cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine instead of thermally. It is. Moreover, a polyimide varnish can be obtained by putting these dehydration cyclization reagents into the polyimide precursor varnish in advance, and heating and stirring if necessary. This can be isolated as a polyimide powder by dropping and filtering in a poor solvent such as water or methanol. Moreover, a polyimide film can also be produced by casting and drying the polyimide varnish on the substrate. This may be further heat-treated.
A polyimide molded body can be produced by heating and compressing the polyimide powder.

Hereinafter, the present invention will be described by way of specific examples. However, the present invention is not limited to these.
[Characteristic evaluation]
Each mechanical property (tensile modulus, elongation, tensile strength) was evaluated by the following method. The results are shown in Table 1.
[Test method]
・ Tensile strength test test method: JIS K7127
Tensile speed: 102 mm / min
Distance between chucks: 30mm
Testing machine: Shimadzu AGS-J

( Reference Example 1)
Under a nitrogen atmosphere, 107.0 g (0.26 mol) of BAPP, 40.81 g (0.13 mol) of ODPA and 37.15 g (0.13 mol) of BPDA were added to 1062.5 g of NMP, The mixture was stirred and reacted at atmospheric pressure for 3 hours to obtain a polyamic acid solution (polyamic acid composition).
The obtained polyamic acid was heated and stirred while removing condensed water from the system at 100 ° C. for 1 hour and at 200 ° C. for 1 hour to obtain a polyimide solution.
15 g of the obtained polyimide solution was applied to a glass plate using a bar coater and dried by heating at 120 ° C. for 30 minutes, 160 ° C. for 15 minutes, and 250 ° C. for 30 minutes to obtain a polyimide film having a thickness of about 25 μm.
The film was subjected to a characteristic evaluation test, and the results are shown in Table 1. In addition, let each component molar ratio be the molar ratio in a wholly aromatic diamine component and a wholly aromatic tetracarboxylic acid component.

(Examples 1 and 2 and Reference Example 2 )
In the same procedure as in Reference Example 1, an aromatic diamine component and an aromatic tetracarboxylic acid component were prepared at a molar ratio shown in Table 1 to produce a polyamic acid and a polyimide film, subjected to a property evaluation test, and Table 1 shows the results. .

(Comparative Examples 1-4)
In the same procedure as in Reference Example 1, an aromatic diamine component and an aromatic tetracarboxylic acid component were prepared at a molar ratio shown in Table 2 to produce a polyamic acid and a polyimide film, subjected to a property evaluation test, and Table 2 shows the results. .

Details of the monomer components shown in each table are as follows.
NMP: N-methyl-2-pyrrolidone BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane ODPA: 4,4′-oxydiphthalic anhydride BPDA: 3,3 ′, 4,4 ′ -Biphenyltetracarboxylic dianhydride

As is clear from the results shown in Table 1 above, the BAPP-ODPA-based polyimide not containing BPDA (Comparative Example 1) and the BAPP-BPDA-based polyimide not containing ODPA (Comparative Example 4) have very low elongation. Also, the tensile strength was low. Further, the polyimide containing 90 mol% OPDA and 10 mol% BDPA (Comparative Example 2) and the polyimide containing 20 mol% OPDA and 80 mol% BPDA (Comparative Example 3) have a very high elongation rate as in Comparative Examples 1 and 4. The tensile strength was low.
In contrast, Examples 1 and 2 have particularly high elongation, high tensile strength, and excellent mechanical strength.

The polyamic acid, polyimide, and these compositions of the present invention have excellent processability, i.e., organic solvent solubility and mechanical strength. These can be used for flexible printed circuit (FPC), chip-on-film (COF), and electronic circuit boards for tape automated bonding (TAB) using these as heat-resistant adhesives.
Polyimide has not only excellent heat resistance but also chemical resistance, radiation resistance, electrical insulation, excellent mechanical properties, etc., so FPC, COF, TAB substrate, semiconductor element protective film, It can be widely used for various electronic devices such as an interlayer insulating film of an integrated circuit.

Claims (4)

To the diamine component consisting of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-oxydiphthalic anhydride: 80 mol% or more , less than 90 mol% and 3,3 ′, 4, 4'-biphenyltetracarboxylic dianhydride: Polyamic acid obtained by polymerizing an acid component composed of 20 mol% or less and more than 10 mol%. To the diamine component consisting of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-oxydiphthalic anhydride: 80 mol% or more , less than 90 mol% and 3,3 ′, 4, 4'-biphenyltetracarboxylic dianhydride: A polyamic acid composition containing a polyamic acid obtained by polymerizing an acid component consisting of 20 mol% or less and more than 10 mol%. To the diamine component consisting of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-oxydiphthalic anhydride: 80 mol% or more , less than 90 mol% and 3,3 ′, 4, 4'-biphenyltetracarboxylic dianhydride: A polyimide obtained by polymerizing an acid component consisting of 20 mol% or less and more than 10 mol%. To the diamine component consisting of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-oxydiphthalic anhydride: 80 mol% or more , less than 90 mol% and 3,3 ′, 4, 4′-biphenyltetracarboxylic dianhydride: A polyimide composition containing a polyimide obtained by polymerizing an acid component consisting of 20 mol% or less and more than 10 mol%.